CN113003669A - Preparation method of fluorine modified titanium suboxide active membrane electrode for electrocatalytic oxidation wastewater treatment and flow-through water treatment mode - Google Patents
Preparation method of fluorine modified titanium suboxide active membrane electrode for electrocatalytic oxidation wastewater treatment and flow-through water treatment mode Download PDFInfo
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Abstract
A preparation method of a fluorine modified titanium monoxide active membrane electrode for electrocatalytic oxidation wastewater treatment and a flow-through water treatment mode relate to the technical field of water treatment. The invention aims to solve the problems of low pollution selectivity and low degradation efficiency caused by pollutant diffusion limitation of active species generated on the surface of an electrode. The invention utilizes the enhanced hydrophobic property of fluorine modified membrane electrode surface to improve the oxygen evolution potential of the titanium suboxide active membrane electrode, increase the yield of hydroxyl free radicals and the selectivity to pollutants, strengthen the mass transfer of pollutants to the electrode surface in a flow-through running mode, accelerate the electrocatalytic oxidation reaction rate and reduce the reaction energy consumption. The method drives and controls the reaction to be carried out by mainly controlling the reaction potential and the water inlet flow, has simple and reliable operation, high efficiency and no secondary pollution in the treatment process, and is suitable for large-scale water treatment application.
Description
Technical Field
The invention belongs to the technical field of water treatment, and particularly relates to a preparation method of a fluorine modified titanium suboxide active membrane electrode for treating electrocatalytic oxidation wastewater and a flow-through water treatment mode.
Background
Tetrabromobisphenol A (TBBPA) as the substituentThe surface bromine flame retardant is widely used in electronic products such as plastic products, rubber, printed circuit boards and the like. The widespread use, persistence, and bioaccumulation of TBBPA have made it ubiquitous in various environmental media as an emerging micropollutant. Meanwhile, the TBBPA degradation technology is urgently needed to be developed as endocrine disruptors and immunotoxic substances are included in a 2A carcinogen list by WHO. At present, TBBPA degradation methods mainly comprise physical methods such as biological method, pyrolysis, adsorption and membrane filtration, and O3UV/Fenton, photocatalysis and the like, and nZVI reduction. The traditional physical and chemical method has the problems of potential secondary pollution, high operation and reagent cost, severe reaction conditions and the like.
In recent years, the electrochemical oxidation method attracts attention due to its unique advantages of high-efficiency cleaning, mild reaction, easy management, suitability for removing refractory pollutants, modular operation, dispersed water treatment and the like. In general, electrochemical oxidation is capable of oxidizing contaminants not only by direct electron transfer to the electrode surface, but also by anodic discharge to generate strong oxidizing radicals, OH (E), in situ at the interface02.38V vs SHE) induced indirect oxidation. Wherein, OH can efficiently oxidize the organic pollutants which are difficult to be biodegraded without selectivity (k is more than 10)8M-1s-1) Therefore, the indirect oxidation can effectively realize the mineralization of the pollutants which are difficult to degrade. However, the OH active species generated out of phase have high reactivity and short half-life, and thus can be physically adsorbed only in a narrow nernst diffusion layer of submicron order near the anode. It can be seen that the efficiency of electrooxidation of nonbiodegradable organic substances depends mainly on the mass transfer rate of the pollutants, the yield of electrolyzed OH and the utilization rate of the electrolyzed OH.
The traditional electrolytic cell uses a flat plate electrode and adopts a flow passing mode, so that the thickness of a diffusion layer can reach 1-2 orders of magnitude of the thickness of a reactive boundary layer. When the current density exceeds the limiting current density, the oxidation reaction of the contaminants is diffusion controlled, which undoubtedly requires a longer hydraulic residence time, i.e. reaction time, thereby increasing the energy consumption to meet the effective removal of the contaminants. In recent years, flow-through porous electrochemical membrane electrodes (REM) have integrated both physical filtration and electrochemical functions. On one hand, the cross-flow mode forcibly compresses the thickness of the diffusion layer through the enhanced convection mass transfer, so that the mass transfer coefficient is remarkably improved by 1-2 orders of magnitude, and the mass transfer limit of the electrooxidation of pollutants is remarkably relieved. On the other hand, the porous electrode can be regarded as a 3-dimensional electrode material, and the active area and the active sites of the electrochemical reaction are obviously improved. Therefore, the flow-through membrane electrode can effectively improve the mass transfer efficiency and fully exert the electrode activity, thereby improving the current efficiency and being expected to become an efficient green process for treating the refractory organic matters in the next generation of water.
Among the reported membrane anode materials, TinO2n-1Ti in (TiSO, 10. gtoreq.n.gtoreq.4)4O7The electrode has the advantages of strong conductivity, relative chemical stability, low cost, oxygen evolution potential (2.6V vs SHE) comparable to that of a BDD electrode and the like, and is widely used for electrochemically oxidizing various pollutants difficult to degrade. However, TiSO anodes still suffer from a deficiency in terms of reactivity, i.e. insufficient yield of free hydroxyl groups, during electrochemical oxidation. Among a plurality of doping materials, researches show that the introduction of F atoms with the strongest electronegativity can redistribute the electron distribution in TiSO, change the Fermi level and adjust the electron transfer property of an electrode, thereby obviously increasing the oxygen evolution overpotential and inhibiting the oxygen evolution side reaction; on the other hand, surface modification of hydrophobic F promotes desorption of OH at the interface, making it more reactive. Therefore, the fluorine modified TiSO membrane electrode (TiSOs-REM) is expected to endow the electrode with new characteristics, thereby being expected to enhance the mass transfer, simultaneously improve the electrode oxygen evolution potential, OH utilization rate and mineralization efficiency, improve the biodegradability and current efficiency of wastewater treatment, and further solve the problem of excessive energy consumption in electrochemical wastewater treatment.
Disclosure of Invention
The invention aims to improve the hydrophobic property and the oxygen evolution potential of the surface of the electrode to reduce the oxygen evolution side reaction in the reaction process and enhance the selectivity of electrocatalytic oxidation on the treatment of pollutants in water by carrying out fluorine modification on the titanium suboxide active membrane electrode. The invention can enhance the degradation efficiency of the polluted water body and achieve the aim of reducing energy consumption.
The invention discloses a preparation method of a fluorine modified titanium monoxide active membrane electrode for treating electrocatalytic oxidation wastewater, which is characterized by comprising the following steps of:
firstly, preparing a titanium suboxide active membrane electrode: using carbon powder as pore generation agent and TiO2The hydrogen flow rate is 200 to 300 mL/min-1Carrying out reduction reaction for 3.5-4.5 h at the temperature of 1000-1100 ℃ to prepare titanium monoxide powder, adding a binder with the mass concentration of 0.5-3% into the obtained titanium monoxide powder material to carry out size mixing, putting the paste after size mixing into a mould to carry out extrusion forming, and then carrying out vacuum drying and roasting to prepare the tubular titanium monoxide active membrane electrode; wherein the addition amount of the binder is 7-10% of the mass of the titanium oxide powder;
secondly, preparing the fluorine modified titanium oxide active membrane electrode: in the reaction tank, a titanium suboxide active membrane electrode is used as an anode, a stainless steel net is used as a cathode, and 0.05-0.15M NaClO is used4Adding NaF into the reaction tank as an electrolyte at a molar ratio of Ti to F of 20: 1-5: 1, wherein the NaF is added at a concentration of 4-6 ml.L-1Polytetrafluoroethylene, and then carrying out current density of 10-30 mA-cm on the anode at the water bath temperature of 80 DEG C-2And performing electrofluorination treatment on the anode with the potential of 2.7-3.4V vs SHE for 50-70 min, and reacting to obtain the fluorine modified titanium oxide active membrane electrode with the atomic content of 0.2-0.5%.
Further, the TiO is2The content of the rutile phase is 80-95%.
Furthermore, the reaction tank is an H-shaped reaction tank, and the anode chamber and the cathode chamber are communicated with each other.
Further, the binder is PVA, PP or CMC.
Further, the molar ratio of Ti to F is 20: 1-5: 1.
Further, the electrofluorination method is to carry out current density of 20-30 mA-cm on the anode at the water bath temperature of 80 DEG C-2And electrolyzing the SHE at an anode potential of 3.0-3.4V vs for 50-60 min.
Further, the roasting temperature in the first step is 400-500 ℃, and the roasting time is 2-4 hours.
Further, the vacuum drying conditions were: drying for 14-18 h at 60 ℃ and a vacuum degree of 80-95 Kpa.
Furthermore, the fluorine atom content in the fluorine modified titanium oxide active membrane electrode is 0.2-0.5%.
The method for constructing the flow-through electrochemical water treatment mode by adopting the fluorine modified titanium oxide active membrane electrode is carried out according to the following modes:
taking the fluorine modified titanium monoxide active membrane electrode as an anode, and a stainless steel mesh surrounding the fluorine modified titanium monoxide active membrane electrode in a sleeve shape as a cathode, wherein the distance between the fluorine modified titanium monoxide active membrane electrode and the stainless steel mesh is 0.5-1 cm, and adding a simulated pollutant, 0.05-0.15M NaClO4As electrolyte, the simulated pollutant water is distributed through the inside of the membrane electrode by a peristaltic pump and flows through, the simulated pollutant water is extracted from the top end of the membrane electrode, and the tail end effluent is recycled, so that the flow-through water treatment mode is constructed and completed; wherein, in the reaction process, the membrane flux range is 0-1628 LHM, and the anode potential range is 0-3.75V vs SHE.
Further, the water distribution of the simulated pollutant is the simulated water distribution of terephthalic acid with the concentration of 1mM and tetrabromobisphenol A with the concentration of 6.44 mu M respectively. Once the membrane electrode is introduced, the membrane electrode is forced to flow through under the pumping action of a peristaltic pump, so that the purpose of mass transfer enhancement is realized.
Further, the flow-through water treatment mode uses direct current as a power supply.
The Terephthalic Acid (TA) is an effective probe of an active species OH, 2-Hydroxy Terephthalic Acid (HTA) is a conversion product between the two, and the conversion product can be used for carrying out quantitative analysis on the generated OH, and the reaction rate constant between the OH and the TA is k.OH,TA＝4.4×109M-1s-1。
The tetrabromobisphenol A (TBBPA) is a typical brominated flame retardant and belongs to a highly lipophilic hydrophobic brominated aromatic compound (logK)ow4.5-5.3), is a chemically stable pollutant with neurotoxicity, genotoxicity and endocrine disrupting toxicity.
The reaction considers that the energy consumption is mainly the electric energy consumed in the process of degrading pollutants, and the electric energy used for providing water circulation by a peristaltic pump is not included.
When the membrane flux in the reaction process is 0LHM, no water body flows through the membrane electrode, the process mainly belongs to a pollutant diffusion control process, and the electrocatalytic oxidation belongs to a sequencing batch water treatment mode. With the increase of the membrane flux, a flow-through water treatment mode is started, namely, the mass transfer capacity is improved, and the electrocatalytic oxidation process is changed from a pollutant diffusion control process to an electrocatalytic oxidation kinetics control process.
In the electrochemical catalytic oxidation process, when the potential is less than 2.38V vs SHE, the electrochemical direct oxidation is carried out, namely, a direct electron transfer process occurs. When the potential is more than 2.38V vs SHE, the method belongs to an indirect oxidation process, namely, an electrogenerated active species hydroxyl radical (. OH) can be generated to participate in pollution oxidation, and the reaction rate constant between the electrogenerated active species hydroxyl radical (. OH) and TBBPA is k.OH,TBBPA＝4.81×109M-1s-1。
The invention has the following beneficial effects:
(1) the method adopts an electrochemical fluorination method to carry out in-situ anodic electrolytic modification on the TiSOs-REM electrode, overcomes the problems of consumption of a large amount of precursor substrates in the previous fluorine modification process and consumption of concentrated acid reagents for adjusting pH in the modification process, has simple and controllable reaction conditions, and is convenient for large-scale production and application.
(2) The fluorine modification method changes the electron distribution in the TiSO electrode, changes the Fermi level structure, adjusts the electron transfer property of the electrode and inhibits the oxygen evolution side reaction, thereby obviously improving the oxygen evolution potential of the membrane electrode; on the other hand, the hydrophobicity of the surface of the electrode is enhanced, and the utilization rate of the electrogenerated active free radicals is improved, so that the efficiency of electrocatalytic oxidation is enhanced, the energy consumption is reduced, and the current efficiency is improved.
(3) The invention greatly enhances the mass transfer of the water body, improves the contact between the polluted water body and the surface of the electrode, avoids the influence of short service life and diffusion limitation of active species generated on the surface of the electrode and enables the electro-catalytic oxidation pollutants to be more selective by a flow-through water treatment mode of the F-TiSOs-REM membrane electrode.
(4) The invention can effectively treat organic pollutants which are strong in toxicity and difficult to degrade until the organic pollutants are finally mineralized, does not generate other toxic and harmful substances in the treatment process, and has the advantages of stable operation, small occupied area and simple operation.
Drawings
FIG. 1 is a graph showing the fluorine atom percentage content in modified F-TiSOs-REM membrane electrodes at different Ti/F molar ratios;
FIG. 2 is an SEM of F-TiSOs-REM membrane electrodes with different atomic percentages of fluorine modification; wherein A is 0% fluorine modified atomic percentage, B is 0.2% fluorine modified atomic percentage, C is 0.5% fluorine modified atomic percentage, and D is 2.5% fluorine modified atomic percentage;
FIG. 3 is an EDS energy spectrum of F-TiSOs-REM; the four figures are respectively a total element mapping diagram and energy spectrum diagrams of elements oxygen (O), titanium (Ti) and fluorine (F);
FIG. 4 is an XRD pattern of F-TiSOs-REM membrane electrodes with different fluorine modification atomic percentages:
FIG. 5 is a fine XPS plot of (G) Ti, (H) O, (I) F in F-TiSOs-REM membrane electrodes with different fluorine modification atomic percentages: wherein, the atom percentage of fluorine modification from bottom to top is 0%, 0.2%, 0.5% and 2.5% in sequence.
FIG. 6 is a graph of contact angles of F-TiSOs-REM membrane electrode surfaces at different fluorine modification atomic percentages; wherein J is 0% fluorine modified atomic percent, K is 0.2% fluorine modified atomic percent, L is 0.5% fluorine modified atomic percent, and M is 2.5% fluorine modified atomic percent;
FIG. 7 is an oxygen evolution potential diagram of F-TiSOs-REM membrane electrodes with different fluorine modification atomic percentages; wherein A is a titanium oxide oxygen evolution potential curve, B is a titanium oxide oxygen evolution potential curve with 0.2% of fluorine modified atom percentage, C is a titanium oxide oxygen evolution potential curve with 0.5% of fluorine modified atom percentage, and D is a titanium oxide oxygen evolution potential curve with 2.5% of fluorine modified atom percentage;
FIG. 8 is an ESR test chart of a TiSOs-REM and F-TiSOs-REM membrane electrode having a fluorine-modified atomic percentage of 0.5%;
FIG. 9 is a schematic view of a reaction apparatus according to the present invention;
FIG. 10 is a graph of TiSOs-REM and F-TiSOs-REM membrane electrode sequencing batch water treatment mode degradation treatment (A) terephthalic acid (TA, radical quencher) and (B) TBBPA; wherein □ represents titanium oxide, and O represents titanium oxide having a fluorine-modified atomic percentage of 0.5%;
FIG. 11 is a graph of COD removal rate and OH utilization rate of TA (A) and its COD removal rate (B) in a cross-flow water treatment mode under different potential conditions; wherein E is titanium oxide, and F is titanium oxide with fluorine modification atom percentage of 0.5%;
FIG. 12 degradation of (A) TBBPA and its (B) COD removal rate and energy consumption in a crossflow water treatment mode under different potential conditions; wherein E is titanium oxide, and F is titanium oxide with fluorine modification atom percentage of 0.5%;
FIG. 13 is a graph of (A) the apparent rate of TBBPA, (B) the amount of debromination, (C) the COD removal rate and (D) the energy consumption for a cross-flow water treatment model degradation under different membrane flux conditions; wherein E is titanium oxide, and F is titanium oxide with fluorine modification atom percentage of 0.5%.
Detailed Description
It will be understood by those of ordinary skill in the art that the foregoing embodiments are specific examples for carrying out the invention, and that various changes in form and details may be made therein without departing from the spirit and scope of the invention in practice.
To make the objects, aspects and advantages of the embodiments of the present invention more apparent, the following detailed description clearly illustrates the spirit of the disclosure, and any person skilled in the art, after understanding the embodiments of the disclosure, may make changes and modifications to the technology taught by the disclosure without departing from the spirit and scope of the disclosure.
The exemplary embodiments of the present invention and the description thereof are provided to explain the present invention and not to limit the present invention.
Examples
Preparing a titanium suboxide active membrane electrode (TiSOs-REM): using carbon powder as pore generation agent and TiO2At a hydrogen flow rate of 250ml min-1And carrying out reduction reaction for 4h at 1050 ℃ to prepare titanium protoxide powder (TiSOs). Adding binder into the TiSOs powder material, mixing, and extruding the paste in a dieAnd after forming, carrying out vacuum drying and high-temperature roasting to obtain the tubular membrane electrode TiSOs-REM, wherein the length of the tubular membrane electrode TiSOs-REM is 6.4cm, the inner diameter of the tubular membrane electrode TiSOs-REM is 2.4cm, the outer diameter of the tubular membrane electrode TiSOs-REM is 2.9cm, and the thickness of the tubular membrane electrode TiSOs-REM is.
Preparing a fluorine modified titanium oxide active membrane electrode (F-TiSOs-REM): in the reaction tank, TiSOs-REM is used as an anode, a stainless steel net is used as a cathode, and the reaction tank contains 5ml of L-10.1M NaClO of Polytetrafluoroethylene (60 wt% PTFE)4As an electrolyte. As shown in FIG. 1, a Ti/F molar ratio of 40: the concentration of NaF corresponding to 1-3: 1, and the current density of the TiSOs-REM anode is 20mA cm at the water bath temperature of 80 DEG C-2Performing electrofluorination for 60min, and reacting to obtain F-TiSOs-REM with the fluorine modification atomic ratio of 0.0-2.5%. Wherein the Ti/F molar ratio has a significant effect on the fluorine modification ratio of the titanium suboxide, which is noteworthy that the Ti/F molar ratio is only between 20: 1-3: 1, the electro-deposition modification of the titanium oxide substrate can be shown, and the smaller the Ti/F molar ratio is, the higher the F-TiSOs-REM fluorine modification ratio obtained under the same condition is.
As shown in FIGS. 2 to 6, the surface morphology of F-TiSOs-REM is porous and does not change with F modification, and the same situation is obtained in the XRD crystal phase structure analysis test. The surface element distribution and XPS test can show that the F element is successfully modified on the surface, and the corresponding fine spectrogram peak intensity of the F element is improved along with the improvement of the atomic percentage of the modified F element. Most notably, in the contact angle test, as the atomic percentage of F modification is increased, the initial contact angle is increased from 63.2 + -2.4 degrees to 133.5 + -3.4 degrees, and the hydrophobicity of the surface of the F-TiSOs-REM membrane electrode is also increased.
As shown in FIG. 7, as the atomic percentage of F modification is increased from 0.0% to 2.5%, the oxygen evolution potential of the F-TiSOs-REM membrane electrode is also increased from the initial 2.1V vs SHE to the final 2.7V vs SHE, and the increase of the oxygen evolution potential of the membrane electrode helps to reduce the occurrence of side reactions during the electrocatalytic oxidation process. It is worth noting that when the percentage of modified atoms of F is too high, the response current is greatly reduced, and the conductivity of the F-TiSOs-REM electrode is reduced, so that the reasonable range of the percentage of modified atoms of F is 0.2-0.5%, and the corresponding Ti/F molar ratio is 20: 1-5: 1.
As shown in FIG. 8, at a current density of 10mA cm-2In the process, TiSOs-REM (3.93V vs SHE) and F-TiSOs-REM (4.10V vs SHE) membrane electrodes with 0.5% fluorine modified atomic percent can generate active species OH in the electrocatalytic oxidation process, but compared with ESR test signal peak intensity, F-TiSOs-REM membrane electrodes with 0.5% fluorine modified atomic percent can generate more free radicals, which is more beneficial to the degradation of pollutants by the F-TiSOs-REM membrane electrodes.
FIG. 9 is a schematic diagram of a flow-through water treatment model for the construction of F-TiSOs-REM. F-TiSOs-REM with fluorine modified atomic percentage of 0.5% is used as an anode, a stainless steel net surrounds the F-TiSOs-REM in a sleeve shape to be used as a cathode, the distance between the F-TiSOs-REM and the stainless steel net is 0.7cm, Terephthalic Acid (TA) with the concentration of 1mM and tetrabromobisphenol A (TBBPA) with the concentration of 6.44 mu M are respectively used as a simulated pollutant, and 0.1M NaClO is used as a simulated pollutant4As an electrolyte. Raw water is pumped out from the top end of the membrane electrode at different flow rates through a peristaltic pump, the water is forced to flow through the membrane electrode, and the tail end effluent is recycled.
As shown in FIG. 10A, in the sequencing batch water treatment mode for 20min, the current density was 10mA cm-2The removal of TA by TiSOs-REM (3.93V vs SHE) was 22.7% and conversion produced 15.8. mu.M HTA. In contrast, the removal of TA by F-TiSOs-REM (4.10V vs SHE) with 0.5% fluorine-modified atomic percent was increased to 49.6% and the conversion generated HTA as high as 52.1. mu.M. Such similar results were also obtained when treating TBBPA, and the results are shown in fig. 10B. The reaction kinetic rate of F-TiSOs-REM with 0.5% fluorine modified atom percent on TBBPA is improved by 1.1 times compared with TiSOs-REM.
As shown in FIG. 11, when TA is treated in a 20min flow-through water treatment mode, the treatment efficiency of the TA by the membrane flux of 651LMH, TiSOs-REM and F-TiSOs-REM with fluorine modification atomic percentage of 0.5% is greatly improved compared with the treatment efficiency of the TA by the prior sequencing batch, the removal rate of the TA by the TiSOs-REM (3.80V vs SHE) can reach 91.2%, and the removal rate of the TA by the F-TiSOs-REM (3.75V vs SHE) can reach 99.5%. In addition, in the flow-through mode, when the potential range is 0-3.75V vs SHE, the TA treatment efficiency and COD treatment efficiency of TiSOs-REM and F-TiSOs-REM are improved along with the increase of the potential, but the treatment effect of F-TiSOs-REM is better than that of TiSOs-REM under any potential test. It should be noted that when the potential reaches 3.75V vs SHE, the utilization efficiency of OH by F-TiSOs-REM with 0.5 atomic percent of fluorine modification can reach 100%, ensuring that the active species is more selective for oxidative decomposition of organic pollutants, while the utilization efficiency of OH by TiSOs-REM is only 38.0%.
As shown in fig. 12, when TBBPA is treated in a 20min flow-through water treatment mode and the membrane flux is 651LMH, the same treatment effect can be achieved in the flow-through mode for 20min, in other words, the reaction rate can be increased by 3.75 times of the original rate, compared with the treatment effect of F-TiSOs-REM in a sequencing batch mode for 75 min. And the same as the TA treatment process, in the flow-through mode, when the potential range is 0-3.75V vs SHE, the treatment efficiency of the TiSOs-REM and the F-TiSOs-REM with the fluorine modified atomic percentage of 0.5 percent on TBBPA and the treatment efficiency of COD are improved along with the increase of the potential, but the treatment effect of the F-TiSOs-REM with the fluorine modified atomic percentage of 0.5 percent is better than that of the TiSOs-REM under any potential test.
As shown in FIG. 13, when F-TiSOs-REM with 0.5% fluorine-modified atomic percentage at a potential of 3.75V vs SHE was used to treat TBBPA in flow-through mode, different membrane fluxes affected the treatment effect, including the mass transfer coefficient, the Br removal effect, the COD removal efficiency, and the power consumption. Along with the improvement of the membrane flux, the mass transfer coefficient, the Br removal effect and the COD removal efficiency are also obviously improved, and the energy consumption is also obviously reduced. The results of all the above parameter tests prove that F-TiSOs-REM with 0.5 percent of fluorine modified atom percentage is also obviously superior to TiSOs-REM.
Claims (10)
1. A preparation method of a fluorine modified titanium monoxide active membrane electrode for electrocatalytic oxidation wastewater treatment is characterized by comprising the following steps:
preparation of titanium monoxide active membrane electrodePreparing: using carbon powder as pore generation agent and TiO2The hydrogen flow rate is 200 to 300 mL/min-1Carrying out reduction reaction for 3.5-4.5 h at the temperature of 1000-1100 ℃ to prepare titanium monoxide powder, adding a binder with the mass concentration of 0.5-3% into the obtained titanium monoxide powder material to carry out size mixing, putting the paste after size mixing into a mould to carry out extrusion forming, and then carrying out vacuum drying and roasting to prepare the tubular titanium monoxide active membrane electrode; wherein the addition amount of the binder is 7-10% of the mass of the titanium oxide powder;
secondly, preparing the fluorine modified titanium oxide active membrane electrode: in the reaction tank, a titanium suboxide active membrane electrode is used as an anode, a stainless steel net is used as a cathode, and 0.05-0.15M NaClO is used4Adding NaF into the reaction tank as an electrolyte at a molar ratio of Ti to F of 20: 1-5: 1, wherein the NaF is added at a concentration of 4-6 ml.L-1Polytetrafluoroethylene, and then carrying out current density of 10-30 mA-cm on the anode at the water bath temperature of 80 DEG C-2And performing electrofluorination treatment on the anode with the potential of 2.7-3.4V vs SHE for 50-70 min, and reacting to obtain the fluorine modified titanium oxide active membrane electrode with the atomic content of 0.2-0.5%.
2. The method for preparing fluorine modified titanium oxide active membrane electrode for electrocatalytic oxidation wastewater treatment according to claim 1, wherein the TiO is prepared by using a titanium oxide-containing solution2The content of the rutile phase is 80-95%.
3. The method for preparing the fluorine-modified titanium monoxide active membrane electrode for electrocatalytic oxidation wastewater treatment as set forth in claim 1, wherein the reaction cell is an H-type reaction cell, and the anode chamber and the cathode chamber are communicated with each other.
4. The method for preparing a fluorine modified titanium monoxide active membrane electrode for electrocatalytic oxidation wastewater treatment as claimed in claim 1, wherein the binder is PVA, PP or CMC.
5. The method for preparing the fluorine modified titanium monoxide active membrane electrode for the electro-catalytic oxidation wastewater treatment according to claim 1, wherein the molar ratio of Ti to F is 20: 1-5: 1.
6. The method for preparing the fluorine-modified titanium monoxide active membrane electrode for the electro-catalytic oxidation wastewater treatment according to claim 1, wherein the electro-fluorination method comprises the step of carrying out the current density of 20-30 mA-cm on the anode at the water bath temperature of 80 ℃-2And electrolyzing the SHE at an anode potential of 3.0-3.4V vs for 50-60 min.
7. The preparation method of the fluorine modified titanium monoxide active membrane electrode for the electrocatalytic oxidation wastewater treatment according to claim 1, wherein the roasting temperature in the step one is 400-500 ℃, and the roasting time is 2-4 hours.
8. The method for constructing a flow-through electrochemical water treatment mode by adopting the fluorine-modified titanium monoxide active membrane electrode as claimed in claim 1 is characterized by being carried out in the following way:
taking the fluorine modified titanium monoxide active membrane electrode as an anode, and a stainless steel mesh surrounding the fluorine modified titanium monoxide active membrane electrode in a sleeve shape as a cathode, wherein the distance between the fluorine modified titanium monoxide active membrane electrode and the stainless steel mesh is 0.5-1 cm, and adding a simulated pollutant, 0.05-0.15M NaClO4As electrolyte, the simulated pollutant water is distributed through the inside of the membrane electrode by a peristaltic pump and flows through, the simulated pollutant water is extracted from the top end of the membrane electrode, and the tail end effluent is recycled, so that the flow-through water treatment mode is constructed and completed; wherein, in the reaction process, the membrane flux range is 0-1628 LHM, and the anode potential range is 0-3.75V vs SHE.
9. A method of constructing a flow-through water treatment model as set forth in claim 8 wherein the simulated contaminant distribution is simulated distribution of terephthalic acid at a concentration of 1mM and tetrabromobisphenol a at a concentration of 6.44 μ M, respectively.
10. The method of claim 8, wherein said flow-through water treatment mode uses direct current as a power source.
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